Nanostructure, electrochemistry and potential-dependent lubricity of the catanionic surface-active ionic liquid [P_6,6,6,14] [AOT]

Hypothesis: A catanionic surface-active ionic liquid (SAIL) trihexyltetradecylphosphonium 1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate ([P_6,6,6,14] [AOT]) is nanostructured in the bulk and at the interface. The interfacial nanostructure and lubricity may be changed by applying a potential. Experiments: The bulk structure and viscosity have been investigated using small angle X-ray scattering (SAXS) and rheometry. The interfacial structure and lubricity as a function of potential have been investigated using atomic force microscopy (AFM). The electrochemistry has been investigated using cyclic voltammetry. Findings: [P_6,6,6,14] [AOT] shows sponge-like bulk nanostructure with distinct interdigitation of cation–anion alkyl chains. Shear-thinning occurs at 293 K and below, but becomes less obvious on heating up to 313 K. Voltammetric analysis reveals that the electrochemical window of [P_6,6,6,14] [AOT] on a gold micro disk electrode exceeds the potential range of the AFM experiments and that negligible redox activity occurs in this range. The interfacial layered structure of [P_6,6,6,14] [AOT] is weaker than conventional ILs and SAILs, whereas lubricity is better, confirming the inverse correlation between the near-surface structure and lubricity. The adhesive forces of [P_6,6,6,14] [AOT] are lower at −1.0 V than at open circuit potential and +1.0 V, likely due to reduced electrostatic interactions caused by shielding of charge centres via long alkyl chains.